In 1970 Gibson and co-workers reported the enantioselective oxidation of toluene to cis-toluenediol [(+)-cis-2,3-dihydroxylmethylcyclohexa-4,6-diene] by a mutant of Pseudomonas putida, a soil bacterium [Gibson et al., J. Biochemistry 9:1626 (1970)]. Since that time many other simple arenes were shown to yield diols of this type through microbial oxidation techniques [Jerina et al., Arch. Biochem. Biophys. 142:394 (1971); Gibson et al., Biochemistry 7:3795 (1968); Jeffrey et al., Biochemistry 14:575 (1975); Burlingame et al., J. Bacteriol. 168:55 (1986); Gibson et al., Biochem. Biophys. Res. Commun. 50:211 (1973); Gibson et al., J. Bacteriol. 119:930 (1974); Whited et al., J. Bacteriol. 166:1028 (1986); Ziffer et al., Tetrahedron 33:2491 (1977)].
Despite the operational simplicity and complete stereospecificity of the reaction producing such diols, little use of this transformation has been made in organic synthesis, except for a few recent reports. [See for example: Hudlicky et al., J. Am. Chem. Soc. 110:4735 (1988) (used the toluene diol to synthesize enones useful for prostaglandin synthesis, aldehydes which are potential synthons for perhydroazulene terpenes, and cyclohexene oxide which is the descarbobenzoxy derivative of crotepoxide); Hudlicky et al., J. Org. Chem. 54:4239 (1989) (used the styrene diol to synthesize zeylena, cyclohexene oxide); Ley et al., Tetrahedron Letters 28:225 (1987) and Tetrahedron Letters 29:5305 (1988) (used the benzene diol to synthesize (+)-pinitol and inositol-1,4,5-triphosphate, respectively); and Johnson and Penning, J. Am. Chem. Soc. 108:4735 (1986) (reported a four step enantioselective synthesis of a prostaglandin intermediate in the shortest route to PGE2a, which was obtained by combination of the microbially derived chiral pool reagents with Johnson's procedure for the attachment of prostaglandin side chains)]. However, the full potential of such diols for synthesis of chiral synthons has not yet been fully realized.
At present, most commercially produced sugars (such as tetroses, pentoses, hexoses, polysaccharides, and derivatives thereof) are derived from natural sources or are produced by arduous chemical synthesis from other sugars. L-sugars have been particularly difficult to obtain by presently available synthetic means. The currently available processes for production of sugars and their derivatives have proven relatively inefficient and expensive. Thus, there is a need for a simple, efficient and cost effective method for synthesizing sugars and derivatives thereof, as well as for making other chiral synthons from readily available materials which can be transformed into the appropriate diols.
Currently, the well-accepted chiron approach to synthesis has relied on sugars, amino acids, or terpenoids as sources of chirality, but the crossover from one enantiomeric series to another almost always requires some redesign of the synthesis and the regeneration of the appropriate enantiomer of the starting material. [See for example: (a) Hanessian, S. Total Synthesis of Natural Products: The Chiron Approach. Baldwin, J. E., Ed.; Organic Chemistry Series, Vol. 3; Pergamon: Oxford, 1983. (b) MacGarvey, G. J., Williams, J. M. J. Am. Chem. Soc. 1985, 107, 1435; (c) Hanessian, S. Aldrichimica Acta, 1989, 22, 3.] Alternatively, the carbohydrate manifold has been reached from acyclic precursors in the approaches of Danishefsky [Bimwala, M.; de Guchteneere, E.; Vieira, E.; Wagner, J. Trends in Synthetic Carbohydrate Chemistry, Horton, D., Hawkins, L. D., McGarvey, G. J., eds., ACS Symposium Series, 1989, 386, 197] and Schmidt [Schmidt, R. R. Trends in Synthetic Carbohydrate Chemistry, Horton, D., Hawkins, L. D., McGarvey, G. J., eds., ACS Symposium Series, 1989, 386, 183] or from cyclic compounds in the approaches of Vogel [Vogel, P.; Auberson, Y.; Bimwala, M.; de Guchteneere, E.; Vieira, E.; Wagner, J. Trends in Synthetic Carbohydrate Chemistry, Horton, D., Hawkins, L. D., McGarvey, G. J., eds., ACS Symposium Series, 1989, 386, 197].